Polymerizable composition and cured resin composition

ABSTRACT

It is an object of the present invention to provide a polymerizable composition and a cured resin composition, linear expansion coefficients of which are significantly improved without impairment of the excellent properties such as heat resistance, mechanical strength and the like of norbornene-based resins. The present invention is a polymerizable composition, which comprises a polymerizable substance containing a norbornene-based monomer or oligomer as a main component, a metathesis polymerization catalyst and silica powder, the weight content of the silica powder being larger than the weight content of the polymerizable substance.

TECHNICAL FIELD

The present invention relates to a polymerizable composition and a curedresin composition, linear expansion coefficients of which aresignificantly improved without impairment of the excellent propertiessuch as heat resistance, mechanical strength and the like ofnorbornene-based resins.

BACKGROUND ART

Conventionally, it has been known that norbornene-based monomers yieldpolymers by a metathesis polymerization reaction. In particular, thereis employed a method of obtaining norbornene-based resin molded articlesaccording to a so-called reaction injection molding (RIM) method inwhich polymerization and molding are simultaneously performed in onestep in a die in the presence of a metathesis polymerization catalystusing a norbornene-based monomer which is cheaply available likedicyclopentadiene and the like.

In accordance with this RIM method, large molded articles can beattained using a cheap mold for low pressure molding and, further, theresulting molded articles have the good balance between rigidity andimpact resistance. Accordingly, it can be said that the RIM method isone of highly practical molding means which can attain attractive moldedarticles. Particularly, in recent years, this method is expected to beapplied to the uses of insulating substrate materials such as a printedcircuit board, a laminate, copper foil with resin, a thin copper cladlaminate, a polyimide film, a film for Tape Automated Bonding (TAB) andthe like, and of sealing resins which seal the periphery of connectingportions in order to secure the strength of connection in the case ofmaking electric connections between substrates or between a substrateand an electronic device.

However, even though uses, which needed higher rigidity and a lowerlinear expansion coefficient like this, increased and, correspondingly,enhanced rigidity and reduced linear expansion coefficient have beenever more required, these properties could not be adequately improved inbalance by the conventional RIM method.

For this situation, various solving means have been proposed in order toachieve the enhanced rigidity and reduced linear expansion coefficientof the norbornene-based resin molded articles. An example of typicalmeans may include a method of blending a reinforced fiber or a filler.For example, Japanese Kokai Publication Hei-10-17676 disclosesa-technique of obtaining a norbornene-based resin molded article bycuring a norbornene-based resin composition which contains a particulatefiller surface-treated in advance with a silane coupling agent, in thepresence of a fiber reinforced material surface-treated in advance witha silane coupling agent. In accordance with this method, a moldedarticle of the norbornene-based resin can be obtained with enhancedrigidity and reduced linear expansion coefficient. However, this methodpresented a problem that productivity would be deteriorated due to thenecessity of surface treatment of the filler in advance and, also, aproblem that when a filler was charged in a large amount, thenorbornene-based resin composition would not flow well because ofincreased viscosity; therefore, compounded liquid would not flow everyhole and corner of a mold. Further, it presented a problem that sinceair bubbles in the norbornene-based resin composition are hard todeaerate, mechanical properties of the molded article, particularly,mechanical strength is deteriorated.

Thus, it has been strongly required to develop a norbornene-based resincomposition providing norbornene-based resin molded articles which havehigh fluidity and good mechanical properties even though blendingconventional reinforced fiber or filler in a large amount.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide a polymerizablecomposition and a cured resin composition, linear expansion coefficientsof which are significantly improved without impairment of the excellentproperties such as heat resistance, mechanical strength and the like ofnorbornene-based resins.

A first aspect of the present invention concerns a polymerizablecomposition which comprises a polymerizable substance containing anorbornene-based monomer or oligomer as a main component, a metathesispolymerization catalyst, and silica powder, the weight content of thesilica powder being larger than the weight content of the polymerizablesubstance. Preferably, the polymerizable composition according to thefirst aspect of the present invention, which further comprises aglycerin fatty acid ester, a polyglycerin polyricinoleate ester or atitanate-based coupling agent.

The silica powder is preferably a surface treatment silicasurface-treated with a fatty acid or a fatty acid ester. In addition,the silica powder is preferably contained in an amount of 200 to 1,000parts by weight with respect to 100 parts by weight of the polymerizablesubstance.

A cured resin composition, which has a crosslinking structure formed bycuring the polymerizable composition according to the first aspect ofthe present invention, the average linear expansion coefficient at atemperature of 20 to 100° C. being 3×10⁻⁵/° C. or less is also one ofthe first aspect of the present invention.

A second aspect of the present invention concerns a cured resincomposition, which has a crosslinking structure formed by curing thepolymerizable composition containing a polymerizable substancecontaining a norbornene-based monomer or oligomer as a main component,the average linear expansion coefficient at a temperature of 20 to 100°C. being 3×10⁻⁵/° C. or less, the bending strength measured according toa method specified in JIS K 7055 being 15 GPa or more, and thedielectric constant being 3.5 or less. In the cured resin compositionaccording to the second aspect of the present invention, it is preferredthat the water absorption after immersing for 24 hours in water of 23°C. is 1% by weight or less.

DETAILED DISCLOSURE OF THE INVENTION

Hereinafter, the present invention will be described in detail.

As a result of studying intensely, the present inventors have found thatwhen silica powder is selected as a filler to be added to apolymerizable substance and a metathesis polymerization catalyst, it ispossible to attain a composition having the viscosity of the order ofbeing adequately moldable even though blending the silica powder in alarge amount to a degree that the weight content of the silica powder islarger than the weight content of the polymerizable substance so as tobe capable of improving significantly a linear expansion coefficient andthe like, leading to the completion of the present invention.Furthermore, as a result of studying intensely, the present inventorshave found that when a specific dispersant is used in combination withthe silica powder, it is possible to attain a composition having theviscosity of the order of being adequately moldable even though blendingan unbelievably large amount of the silica powder.

A polymerizable resin composition according to the first aspect of thepresent invention comprises a polymerizable substance, a metathesispolymerization catalyst and silica powder.

The polymerizable substance contains a norbornene-based monomer oroligomer as the main component. The norbornene-based monomer or oligomeris not particularly limited as long as it has a norbornene ring, butpolycyclic norbornene-based monomers or oligomers, which are tricyclicor morecyclic compounds, are preferable because they yield the articleswhich are superior in heat resistance, low linear expansion coefficientand the like.

Examples of the norbornene-based monomer may include bicyclic compoundssuch as norbornene, norbornadiene and the like; tricyclic compounds suchas dicyclopentadiene, hydroxydicyclopentadiene and the like; tetracycliccompounds such as tetracyclododecene and the like; pentacyclic compoundssuch as a cyclopentadiene trimer and the like; heptacyclic compoundssuch as tetracyclopentadiene and the like; their derivatives having analkyl group such as methyl, ethyl, propyl, butyl and the like, analkenyl group such as vinyl and the like, an alkylidene group such asethylidene and the like, an aryl group such as phenyl, tolyl, naphthyland the like; and their derivatives having a polar group, containing anelement other than carbon and hydrogen, such as an ester group, an ethergroup, a cyano group, a halogen atom, an alkoxycarbonyl group, a pyridylgroup, a hydroxyl group, a carboxylic acid group, an amino group, anacid anhydride group, a silyl group, an epoxy group, an acrylic group, amethacrylic group and the like. In particular, their derivatives havingthe ester group and the acid anhydride group are preferable from theviewpoint of being capable of providing the reactivity throughdeprotection. In addition, tricyclic, tetracyclic and pentacyclicmonomers are preferable in that they are readily available and highlyreactive, and resin molded articles to be obtained have high heatresistance. These norbornene-based monomers may be used alone or incombination of two or more kinds.

Examples of the norbornene-based oligomer may include an oligomer formedby combining several units of the above norbornene-based monomer intoone, and the like. Such norbornene-based oligomers may be formed bycombining the same kinds of norbornene-based monomers or the differentkinds of norbornene-based monomers. These norbornene-based oligomers maybe used alone or in combination of two or more kinds.

Additionally, in order to make the resulting polymerizable compositionaccording to the first aspect of the present invention thermosetting, acrosslinkable norbornene-based monomer or oligomer preferablyconstitutes 10% by weight or more of the above norbornene-based monomeror oligomer contained in the polymerizable substance. The crosslinkablenorbornene-based monomer or oligomer more preferably constitutes 30% byweight or more.

The crosslinkable norbornene-based monomers or oligomers represent apolycyclic norbornene-based monomer or oligomer having two or morereactive double bonds. Specific examples thereof may includedicyclopentadiene, tricyclopentadiene, tetracyclopentadiene and thelike.

The polymerizable substance may contain a monocyclic cycloolefin, whichcan cause ring-opening copolymerization with the norbornene-basedmonomer, such as cyclobutene, cyclopentene, cyclopentadiene,cyclooctene, cyclooctadiene, cyclododecene and the like as a comonomerwithin the limits of not impairing the purpose of the present inventionin order to make the resulting polymerizable composition according tothe first aspect of the present invention thermosetting.

The metathesis polymerization catalyst is not particularly limited aslong as it is the catalyst capable of polymerizing the norbornene-basedmonomer by ring-opening through bulk polymerization, and examplesthereof may include halides, oxy halides, oxides and organic ammoniumsalts of tungsten, molybdenum, tantalum, ruthenium, osmium and the like.In particular, a ruthenium-based metathesis polymerization catalyst issuitable.

As the ruthenium-based metathesis polymerization catalyst, a catalystrepresented by General formula (1), General formula (3), General formula(4) and General formula (5) are suitably used.

In General formula (1), each of R¹ and R² represents hydrogen, analkenyl group having 2 to 20 carbon atoms, an alkyl group having 1 to 20carbon atoms, an aryl group having 6 to 20 carbon atoms, a carboxylgroup having 2 to 20 carbon atoms, an alkoxyl group having 2 to 20carbon atoms, an alkenyloxy group having 2 to 20 carbon atoms, anaryloxy group having 6 to 20 carbon atoms, an alkoxycarbonyl grouphaving 2 to 20 carbon atoms, an alkylthio group having 2 to 20 carbonatoms, or a ferrocene derivative and, these substances described abovemay be substituted for a phenyl derivative having an alkyl group having1 to 5 carbon atoms, a halogen atom or an alkoxyl group having 1 to 5carbon atoms, if required. In addition, R¹ and R² may be identical withor different from each other.

In General formula (1), each of X¹ and X² represents any anionic ligand,preferably Cl or Br, more preferably Cl. X¹ and X² may be identical withor different from each other.

In General formula (1), each of L¹ and L² represents a neutral electrondonor, preferably a phosphoric ligand or an imidazolium compound. L¹ andL² may be identical with or different from each other.

As the phosphoric ligand, phosphine compounds represented by Generalformula (2) are preferable.

In General formula (2), each of R³, R⁴ and R⁵ represents an alkyl grouphaving 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbonatoms and preferably represents a methyl group, an ethyl group, anisopropyl group, a t-butyl group, a cyclohexyl group, a phenyl group, ora substituted phenyl group. Specific examples thereof may includetricyclohexylphosphine, triphenylphosphine, triisopropylphosphine andthe like. R³, R⁴ and R⁵ may be identical with or different from oneanother.

As the imidazolium compound, for example, imidazoline-2-ylidenederivatives or 4,5-dihydroimidazoline-2-ylidene derivatives arepreferable. Specific examples thereof may includeN,N′-dimesitylimidazoline-2-ylidene ligand,N,N′-dimesityl-4,5-dihydroimidazoline-2-ylidene ligand and the like.

In General formula (1), two or three of X¹, X², L¹ and L² may furtherjoin together to form a multidentate chelate ligand.

Further, in General formula (1), L¹ and L², respectively, are shown in atrans-position but they can occupy a cis-coordination depending onbulkiness thereof or in the case where L¹ and L² are identical moleculeand bisdentate.

Furthermore, in General formula (1), X¹ and X², respectively, are shownin a cis-position but they can occupy a trans-coordination in some kindsof L¹ and L².

In General formula (3), each of R⁶ and R⁷ represents hydrogen, analkenyl group having 2 to 20 carbon atoms, an alkyl group having 1 to 20carbon atoms, an aryl group having 6 to 20 carbon atoms, a carboxylgroup having 2 to 20 carbon atoms, an alkoxyl group having 2 to 20carbon atoms, an alkenyloxy group having 2 to 20 carbon atoms, anaryloxy group having 6 to 20 carbon atoms, an alkoxycarbonyl grouphaving 2 to 20 carbon atoms, an alkylthio group having 2 to 20 carbonatoms, or a ferrocene derivative and, these substances described abovemay be substituted for a phenyl derivative having an alkyl group having1 to 5 carbon atoms, a halogen atom or an alkoxyl group having 1 to 5carbon atoms, if required. In addition, R⁶ and R⁷ may be identical withor different from each other.

However, when an alkylsilyl group or an arylsilyl group is used as R⁶,two or more of the same alkyl groups or aryl groups can be selectedredundantly on silicon because of the stability of its complex, and indoing so, a methyl group, an ethyl group, an isopropyl group, a t-butylgroup, a cyclohexyl group and a phenyl group are preferable.Specifically, there are given a trimethylsilyl group, a triethylsilylgroup, a diphenylmethylsilyl group, a dimethyl-t-butylsilyl group, atriisopropylsilyl group and the like. In this case, as R⁷, a t-butylgroup, a n-butyl group, a n-propyl group, an isopropyl group, an ethylgroup, a methyl group, a methoxymethyl group, a ferrocenyl group, atrimethylsilyl group, a phenyl group, a tolyl group, an anisyl group andthe like are preferable from the viewpoint of the stability and theactivity of a complex.

In General formula (3), each of X³ and X⁴ represents any anionic ligand,preferably Cl or Br, more preferably Cl. X³ and X⁴ may be identical withor different from each other.

In General formula (3), each of L³ and L⁴ represents a neutral electrondonor, preferably a phosphoric ligand or an imidazolium compound. L³ andL⁴ may be identical with or different from each other.

As the phosphoric ligand and the imidazolium compound, the substancesdescribed above are given.

Further, in General formula (3), two or three of X³, X⁴, L³ and L⁴ mayfurther join together to form a multidentate chelate ligand.

In General formula (4) or General formula (5), each of R⁸, R⁹, R¹⁰ andR¹¹ represents hydrogen, an alkenyl group having 2 to 20 carbon atoms,an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20carbon atoms, a carboxyl group having 2 to 20 carbon atoms, an alkoxylgroup having 2 to 20 carbon atoms, an alkenyloxy group having 2 to 20carbon atoms, an aryloxy group having 6 to 20 carbon atoms, analkoxycarbonyl group having 2 to 20 carbon atoms, an alkylthio grouphaving 2 to 20 carbon atoms, or a ferrocene derivative and, thesesubstances described above may be substituted for a phenyl derivativehaving an alkyl group having 1 to 5 carbon atoms, a halogen atom or analkoxyl group having 1 to 5 carbon atoms, if required. In addition, R⁸,R⁹, R¹⁰ and R¹¹ may be identical with or different from one another.

In particular, as the R⁸, R¹⁰ and R¹¹, an alkyl group having 1 to 20carbon atoms, a cyclohexyl group, a phenyl group; and a phenylderivatives having an alkyl group having 1 to 5 carbon atoms, analkyloxy group having 1 to 5 carbon atoms, a carboxyl group, analkylsilyl group having 1 to 5 carbon atoms, a hydroxyl group, a nitrogroup, halogen, an amino group having 5 or less carbon atoms, an acetylgroup and an acetoxy group are more preferable. In particular, a phenylgroup, an o-tolyl group, a p-tolyl group, a 2,6-xylyl group, an anisylgroup, a nitrobenzene group, a chlorobenzene group, an o-isopropylphenylgroup, a 2,6-diisopropylphenyl group, an ethyl group, an isopropylgroup, a t-butyl group and a cyclohexyl group are more preferable.

In General formula (4) or General formula (5), each of Y¹, Y² and Y³represents sulfur, oxygen and selenium, preferably sulfur and seleniumelement. Y¹, Y² and Y³ may be identical with or different from oneanother.

In General formula (4) or General formula (5), each of X⁵, X⁶, X⁷ and X⁸represents any anionic ligand, preferably Cl or Br, more preferably Cl.X⁵, X⁶, X⁷ and X⁸ may be identical with or different from one another.

In General formula (4) or General formula (5), each of L⁵, L⁶, L⁷ and L⁸represents a neutral electron donor, preferably a phosphoric ligand oran imidazolium compound. L⁵, L⁶, L⁷ and L⁸ may be identical with ordifferent from one another.

As the phosphoric ligand and the imidazolium compound, the substancesdescribed above are given.

Further, in General formula (4) or General formula (5) , two or three ofX⁵, X⁶, X⁷, X⁸, L⁵, L⁶, L⁷ and L⁸ may further join together to form amultidentate chelate ligand.

A method of producing the ruthenium-based metathesis polymerizationcatalyst represented by General formula (1), General formula (3),General formula (4) and General formula (5) is not particularly limited,and includes, for example, a method in which a raw material such asligand precursors having L¹ to L⁸ and the like is synthesized accordingto a publicly known method and, on the other hand, a raw material of theprecursor of a ruthenium complex is synthesized according to a publiclyknown method, and finally both raw materials are mixed and aligand-exchange reaction is performed to produce the ruthenium-basedmetathesis polymerization catalyst.

The content of the above-mentioned metathesis polymerization catalyst ispreferably 0.0001 to 1 mol % with respect to the norbornene-basedmonomer or oligomer contained in the polymerizable substance. When thiscontent is less than 0.0001 mol %, a polymerization rate of thenorbornene-based monomer or oligomer may be low and impractical. When itis more than 1 mol %, the polymerizable composition is economicallydisadvantageous. The content is more preferably 0.001 to 0.5 mol %, andfurthermore preferably 0.001 to 0.05 mol %.

The above-mentioned silica powder plays a role as a filler in thepolymerizable composition according to the first aspect of the presentinvention and contributes to the higher rigidity and the reduced linearexpansion coefficient. The silica powder does not inhibit apolymerization reaction of a norbornene-based monomer and anorbornene-based oligomer. By using silica powder as a filler, thepolymerizable composition according to the first aspect of the presentinvention can improve the properties such as the linear expansioncoefficient while retaining high moldability even though blending anextremely large amount of the filler.

The silica powder is preferably surface-treated with a fatty acid or afatty acid ester. Thereby, the wettability of the silica powder isimproved and the silica powder can be more uniformly dispersed in thepolymerizable composition.

The fatty acid and fatty acid ester are not particularly limited, andfor example, a ricinoleate ester, a glycerin fatty acid ester and thelike are suitably used. As the above-mentioned ricinoleate ester and theglycerin fatty acid ester, there are given substances similar tosubstances used as a dispersant described below.

The shape of the silica powder is not particularly limited, but it ispreferably spherical in shape. An average particle diameter of thesilica powder is preferably 100 nm to 100 μm, more preferably 1 to 20μm.

In the polymerizable composition according to the first aspect of thepresent invention, the weight content of the silica powder is largerthan the weight content of the polymerizable substance. The amount ofthe silica powder to be blended in the polymerizable compositionaccording to the first aspect of the present invention is preferably 200to 1,000 parts by weight with respect to 100 parts by weight of thepolymerizable substance. When this amount is less than 200 parts byweight, the linear expansion coefficient of the cured resin compositionto be obtained becomes large; therefore, the cured resin composition maynot be suitable for use in which a high precision is required, such assealing of an optical circuit. When it is more than 1,000 parts byweight, the fluidity of the polymerizable composition becomes poor;therefore, handlability and processability may be deteriorated. Theamount is more preferably 500 to 1,000 parts by weight and furthermorepreferably 800 to 1,000 parts by weight. Conventionally, it has beenthought that even though such a large amount of filler was offered to beblended, blending itself was impossible or even though the filler couldbe blended, molding became difficult due to an increase in the viscosityof a composition to be obtained or contrariwise properties such asmechanical strength were impaired. However, in the polymerizablecomposition according to the first aspect of the present invention, byselecting the silica powder as a filler, it is possible to blend thesilica powder in an amount exceeding the weight content of apolymerizable substance. Further, it becomes possible to blend anunbelievably large amount of the silica powder in the case of using aspecific dispersant described below in combination.

Preferably, the polymerizable composition according to the first aspectof the present invention further comprises at least one kind selectedfrom the group consisting of a glycerin fatty acid ester, a polyglycerinpolyricinoleate ester and a titanate-based coupling agent. These play arole as a dispersant to enhance the dispersibility of the silica powder.By using these dispersants in combination, the resulting polymerizablecomposition according to the first aspect of the present invention canretain high moldability even though blending an extremely large amountof the silica powder. Blending of these dispersant is effective inimproving the mechanical and physical properties since this blending hasthe effect of promoting deaeration of the polymerizable composition andallows voids in the cured resin composition to be obtained to decrease.

Examples of the glycerin fatty acid ester may include diglycerindistearate, diglycerin monostearate, diglycerin monooleate, diglycerindioleate, hexaglycerin monostearate, hexaglycerin monooleate,hexaglycerin monomyristate, hexaglycerin monolaurate, hexaglycerinmonocaprylate, hexaglycerin dicaprylate, hexaglycerin hexastearate,hexaglycerin octastearate, decaglycerin monostearate, decaglycerindistearate, decaglycerin pentastearate, decaglycerin decastearate,decaglycerin monooleate, decaglycerin pentaoleate, decaglycerindecaoleate, decaglycerin monomyristate, decaglycerin monolaurate,triglycerin monolaurate, triglycerin monomyristate, triglycerinmonooleate, triglycerin monostearate, pentaglycerin monolaurate,pentaglycerin monomyristate, pentaglycerin trimyristate, pentaglycerinmonooleate, pentaglycerin trioleate, pentaglycerin monostearate,pentaglycerin tristearate, pentaglycerin hexastearate, and the like.These glycerin fatty acid esters may be used alone or in combination oftwo or more kinds.

Examples of the polyglycerin polyricinoleate ester may includetetraglycerin polyricinoleate, hexaglycerin polyricinoleate,pentaglycerin polyricinoleate, and the like. These polyglycerinpolyricinoleate esters may be used alone or in combination of two ormore kinds.

Examples of the titanate-based coupling agent may include triisostearoylisopropyl titanate, di(dioctylphosphate)diisopropyl titanate,didodecylbenzenesulfonyl diisopropyl titanate, diisostearyl diisopropyltitanate, isopropyltris(dioctylpyrophosphate)titanate,bis(dioctylpyrophosphate)oxyacetate titanate,bis(dioctylpyrophosphate)ethylene titanate,tetraisopropylbis(dioctylphosphate)titanate,tetraoctylbis(ditridecylphosphate) titanate, and the like. Thesetitanate-based coupling agents may be used alone or in combination oftwo or more kinds.

In the polymerizable composition according to the first aspect of thepresent invention, the amount of the dispersant to be blended may beappropriately established depending on the amount of the silica powder,and is preferably, but not particularly limited to, 0.1 to 5 parts byweight with respect to 100 parts by weight of the norbornene-basedmonomer or oligomer.

A method of preparing the polymerizable composition according to thefirst aspect of the present invention is not particularly limited, andincludes, for example, a method in which the polymerizable substance andthe dispersant are mixed and stirred, and to this is added apredetermined amount of the silica powder and the mixture is stirred,and to this mixture is added a predetermined amount of the metathesispolymerization catalyst dissolved in an appropriate solvent and theresulting mixture is mixed.

The polymerizable composition according to the first aspect of thepresent invention comprises a polymerizable substance containing anorbornene-based monomer or oligomer as a main component, a metathesispolymerization catalyst and silica powder. Since it contains silicapowder at a high filling rate, by curing it, it is possible to obtainthe cured resin composition which is superior in the heat resistance andthe mechanical strength, and realizes the low linear expansioncoefficient. Furthermore, this polymerizable composition has highfluidity and can be surely poured every hole and corner of a mold eventhough it contains the silica powder in a large amount, so that it canattain excellent norbornene-based resin molded articles by a reactioninjection molding (RIM) method, a casting method or a spin coatingmethod.

The polymerizable composition according to the first aspect of thepresent invention gives molded articles by being cured and, in addition,can be suitably used as a sealing resin which seals the periphery ofconnecting portions in order to secure the strength of connection in thecase of making electric connections between substrates or between asubstrate and an electronic device. Particularly when this polymerizablecomposition is used as a sealing resin, a highly reliable circuit can beprepared without causing peeling or deviation even in the case where apositional precision and a dimensional precision are required as in anoptical circuit (and an integrated circuit) due to the fact thatresidual strain is less and because of high fluidity prior to curing,air bubbles do not remain in a cured article after curing.

When the polymerizable composition according to the first aspect of thepresent invention contains the definite amount of a crosslinkablenorbornene-based monomer or oligomer as the polymerizable composition,it is cured since a polymerization reaction proceeds by aself-exothermic reaction, and a cured resin composition having acrosslinking structure of which an average linear expansion coefficientat a temperature of 20 to 100° C. is 3×10⁻⁵/° C. or less is obtained.Further, in producing the cured resin composition, the polymerizablecomposition may be heated in order to promote the polymerizationreaction.

The present invention also provides a cured resin composition having acrosslinking structure formed by curing such a polymerizable compositionaccording to the first aspect of the present invention, of which anaverage linear expansion coefficient at a temperature of 20 to 100° C.is 3×10⁻⁵/° C. or less.

When the average linear expansion coefficient at a temperature of 20 to100° C. is more than 3×10⁻⁵/° C., peeling and deviation will arise andreliability of a circuit will be deteriorated in the case where thecured resin composition is used for a seal in which a positionalprecision and a dimensional precision are required as in an opticalcircuit (and an integrated circuit).

The second aspect of the present invention concerns a cured resincomposition having a crosslinking structure formed by curing thepolymerizable composition comprising a polymerizable substancecontaining a norbornene-based monomer or oligomer as a main component,wherein the average linear expansion coefficient at a temperature of 20to 100° C. is 3×10⁻⁵/° C. or less, the bending strength measuredaccording to a method specified in JIS K 7055 is 15 GPa or more, and thedielectric constant is 3.5 or less.

When the average linear expansion coefficient at a temperature of 20 to100° C. is more than 3×10⁻⁵/° C., peeling and deviation will arise andreliability of a circuit will be deteriorated in the case where thecured resin composition is used for a seal in which a positionalprecision and a dimensional precision are required as in an opticalcircuit (and an integrated circuit).

When the bending strength is less than 15 GPa, the strength may beinsufficient in the case where the cured resin composition used for aseal in which a positional precision and a dimensional precision arerequired as in an optical circuit (and an integrated circuit).

In addition, when the cured resin composition according to the secondaspect of the present invention is used as a material for an insulatingsubstrate, it is required that its dielectric constant is low. That is,it is necessary to speed a signal transfer rate for a speedup ofinformation processing and the signal transfer rate becomes faster in amaterial having a lower relative dielectric constant; therefore, thematerial having a lower dielectric constant allows the informationprocessing to speed. In a material used for information andcommunication area in which there has been a growing trend of higherfrequencies, since effects on heat generation in a circuit of a printedboard increase and transmission losses become large due to a highfrequency, materials of printed circuit boards, which are low in adielectric dissipation factor and a relative dielectric constant, cantransfer signals more efficiently, that is, with less transmissionlosses. Further, when the relative dielectric constant is low, there isthe advantage that an insulating layer with thin thickness can bedesigned, and it becomes possible to design a circuit with more widearea compared with a printed circuit board with the same thickness,which is made of a high dielectric constant material and processingbecomes easy. Though epoxy resins have been conventionally used as amaterial for an insulating substrate, the limitations of the dielectricconstant was 3.9 in the epoxy resins. The cured resin compositionaccording to the second aspect of the present invention is formed bypolymerizing the norbornene-based monomer or oligomer and, therefore,could realize a reduced dielectric constant of 3.5 or lower in adielectric constant.

With respect to the cured resin composition according to the secondaspect of the present invention, it is preferred that the waterabsorption after immersing for 24 hours in water of 23° C. is 1% byweight or less. Though the water absorption of epoxy resinsconventionally used in materials for insulating substrates was 1% byweight or more, materials having the low water absorption have beenrequired since the high water absorption of a substrate or an underfillportion may cause a short in a circuit and a decrease in a processingrate. In the case where the cured resin composition is employed insealing of an optical circuit, since a refractive index of light isvaried due to the presence of water, a material having high waterabsorption decreases in transmission stability and increases inattenuation in optical communications, so that it can not be employed inlarge-capacity long-haul communications. The cured resin compositionaccording to the second aspect of the present invention is superior tothe conventional epoxy resins because its water absorption is 1% byweight or less. The water absorption is more preferably 0.5% by weightor less.

The cured resin composition according to the second aspect of thepresent invention may be produced, for example, by polymerizing thepolymerizable composition according to the first aspect of the presentinvention and curing the resulting polymer. The cured resin compositionaccording to the second aspect of the present invention, having theabove-mentioned properties, has not been present, but it can be readilyproduced when the polymerizable composition according to the firstaspect of the present invention is used.

The cured resin composition according to the first aspect of the presentinvention is one, the linear expansion coefficient of which issignificantly improved without impairment of the heat resistance and themechanical strength which norbornene-based resins have. When thepolymerizable composition according to the first aspect of the presentinvention is used, since it has high fluidity before curing even thoughit contains the silica powder at high charging rate, it has goodmoldability and a molded article is readily obtained with high accuracy.

The cured resin composition according to the second aspect of thepresent invention is suitable for the insulating substrate materialssuch as a printed circuit board, a laminate, copper foil with resin, athin copper clad laminate, a polyimide film, a film for Tape AutomatedBonding (TAB) and the like. Further, on the occasion of molding, thecured resin composition according to the second aspect of the presentinvention may be molded alone, but it can be combined with a reinforcedmaterial such as glass cloth to form a single composite because of highfluidity.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail by way ofexamples, but the present invention is not limited to these examples.

(Metathesis Polymerization Catalyst 1)

18.2 mmol of tricyclohexylphosphine and 9.1 mmol of t-butylacetylenewere added to 5.57 g (9.1 mmol) of dichloro(p-cymene)ruthenium and thismixture was reacted for 7 hours together with 150 ml of toluene undernitrogen flow in a 300 ml flask. A ruthenium-based metathesispolymerization catalyst represented by Formula (6) was obtained byremoving toluene under a reduced pressure after the completion of thereaction and recrystallizing the remainder in a tetrahydrofuran/ethanolsystem.

(Metathesis Polymerization Catalyst 2)

A ruthenium-based metathesis polymerization catalyst represented byFormula (7) (Bis(tricyclohexylphosphine)benzylidene ruthenium(IV)dichloride, made by STREM Chemicals, Inc.) was used.

(Metathesis Polymerization Catalyst 3)

In a 50 ml Schlenk flask, the interior of which was displaced withnitrogen gas, 2 mmol of bis(tricyclohexylphosphine)benzylideneruthenium(IV) dichloride represented by Formula (7) was put, and 20 mlof toluene was-added thereto and the mixture was dissolved. 2.2 mmol ofphenylvinyl sulfide was added to this dissolved solution and the mixturewas stirred at room temperature for 8 hours. A ruthenium-basedmetathesis polymerization catalyst represented by Formula (8) wasobtained by removing a solvent under a reduced pressure after thecompletion of the reaction, washing a resulting solid matter with coldacetone and drying it.

(Metathesis Polymerization Catalyst 4)

In a 50 ml Schlenk flask, the interior of which was displaced withnitrogen gas, 2 mmol of bis(triisopropylphosphine)benzylideneruthenium(IV) dichloride represented by Formula (9), which had beensynthesized according to a method described in J. Am. Chem. Soc., 118,100 (1996), was put. 20 ml of toluene was added thereto and the mixturewas dissolved. 2.2 mmol of phenylvinyl sulfide was added to thisdissolved solution and the mixture was stirred at room temperature for 8hours. A ruthenium-based metathesis polymerization catalyst representedby Formula (10) was obtained by removing a solvent under a reducedpressure after the completion of the reaction, washing a resulting solidmatter with cold acetone and drying it.

EXAMPLE 1

A mixture of 80 parts by weight of dicyclopentadiene (made by MaruzenPetrochemical Co., Ltd.) and 20 parts by weight of tricyclopentadiene(made by Maruzen Petrochemical Co., Ltd.) was used as a norbornene-basedmonomer, and 2 parts by weight of a titanate-based coupling agent(PLENACT KR46B, made by Ajinomoto Fine-Techno Co., Ltd.) was blendedinto this norbornene-based monomer mixture as a dispersant and theblended mixture was mixed and stirred. Next, 300 parts by weight offused silica (FB-24, made by DENKI KAGAKU KOGYO KABUSHIKI KAISHA,average particle diameter: 18 μm) was blended under stirring. Further, apolymerization catalyst solution, which was formed by dissolving 10parts by weight of a ruthenium-based metathesis polymerization catalystof Formula (6) in 200 parts by weight of toluene as a metathesispolymerization catalyst, was added thereto at 25° C. in such a mannerthat the rate of the metathesis polymerization catalyst is 0.0001 mol %with respect to the norbornene-based monomer, and this mixture wasstirred to obtain a polymerizable composition.

The resulting polymerizable composition was poured into a flat platemold and then cured by being heated at 40° C. for 1 hour and 120° C. for1 hour to prepare a flat plate made of a cured resin composition.

With respect to the resulting flat plate made of the polymerizablecomposition and the cured resin composition, the following evaluationswere carried out. The results of evaluations were shown in Table 1.

(Measurement of Viscosity of Polymerizable Composition)

The viscosity of the polymerizable composition was measured using aBrookfield type viscometer.

(Measurement of Bending Strength and Bending Modulus)

The bending strength and the bending modulus of the flat plate weremeasured according to a method specified in JIS K 7055.

(Measurement of Average Linear Expansion Coefficient)

With respect to the flat plate, TMA measurement was carried outaccording to a method specified in JIS K 7197, and the average linearexpansion coefficient in a range of 20° C. to 100° C. was determined.

(Measurement of Water Absorption)

With respect to the flat plate, the water absorption after immersing for24 hours in water of 23° C. was measured according to a method specifiedin JIS K 7209.

(Measurement of Dielectric Constant and Dielectric Dissipation Factor)

With respect to the flat plate, the dielectric constant and thedielectric dissipation factor at each frequency were measured using animpedance analyzer (4291B RF impedance/material analyzer, manufacturedby Agilent Technologies Inc.), and a dielectric test fixture 16453A(sample material specification, diameter: 15 mm or more, thickness: 0.3to 3 mm)

EXAMPLE 2

A flat plate made of a polymerizable composition and a cured resincomposition was obtained by following the same procedure as that inExample 1 except for using a ruthenium-based metathesis polymerizationcatalyst of Formula (7) as a metathesis polymerization catalyst, and theevaluations thereof were carried out. The results of evaluations wereshown in Table 1.

EXAMPLE 3

A flat plate made of a polymerizable composition and a cured resincomposition was obtained by following the same procedure as that inExample 1 except for using a ruthenium-based metathesis polymerizationcatalyst of Formula (7) as a metathesis polymerization catalyst and 2parts by weight of a polyglycerin polyricinoleate ester (CHIRABAZOLH-818, made by Taiyo Kagaku Co., Ltd.) as a dispersant, and theevaluations thereof were carried out. The results of evaluations wereshown in Table 1.

EXAMPLE 4

A flat plate made of a polymerizable composition and a cured resincomposition was obtained by following the same procedure as that inExample 1 except for using a ruthenium-based metathesis polymerizationcatalyst of Formula (8) as a metathesis polymerization catalyst and 2parts by weight of a polyglycerin polyricinoleate ester (CHIRABAZOLH-818, made by Taiyo Kagaku Co., Ltd.) as a dispersant, and theevaluations thereof were carried out. The results of evaluations wereshown in Table 1.

EXAMPLE 5

A flat plate made of a polymerizable composition and a cured resincomposition was obtained by following the same procedure as that inExample 1 except for changing the amount of the fused silica to be mixedfrom 300 parts by weight to 400 parts by weight, and the evaluationsthereof were carried out. The results of evaluations were shown in Table1.

EXAMPLE 6

A flat plate made of a polymerizable composition and a cured resincomposition was obtained by following the same procedure as that inExample 5 except for using a ruthenium-based metathesis polymerizationcatalyst of Formula (7) as a metathesis polymerization catalyst, and theevaluations similar to Example 1 were carried out. The results ofevaluations were shown in Table 1. TABLE 1 Example 1 Example 2 Example 3Composition Monomer Dicyclopentadiene/ Dicyclopentadiene/Dicyclopentadiene/ tricyclopentadiene tricyclopentadienetricyclopentadiene Catalyst Formula (6) Formula (7) Formula (7)Dispersant PLENACT KR46B PLENACT KR46B CHIRABAZOL H-818 Fused silicaFB-24 FB-24 FB-24 Amount of fused silica to 300 300 300 be mixed (partsby weight) Evaluation Viscosity (Pa · s) 0.32 0.31 0.31 Bending strength42.1 43.6 44.0 (MPa) Bending modulus 7.4 7.5 7.5 (GPa) Linear expansion17.0 16.3 16.4 coefficient(×10⁻⁶/° C.) Water absorption (%) 0.10 0.090.07 Dielectric (1 MHz) 2.76 2.76 2.79 constant (100 MHz) 2.80 2.81 2.78(1 GHz) 2.78 2.83 2.81 Dielectric (1 MHz) 0.0012 0.0012 0.0012dissipation (100 MHz) 0.0014 0.0013 0.0012 factor (1 GHz) 0.0012 0.00130.0014 Example 4 Example 5 Example 6 Composition MonomerDicyclopentadiene/ Dicyclopentadiene/ Dicyclopentadiene/tricyclopentadiene tricyclopentadiene tricyclopentadiene CatalystFormula (8) Formula (6) Formula (7) Dispersant CHIRABAZOL PLENACT KR46BPLENACT KR46B H-818 Fused silica FB-24 FB-24 FB-24 Amount of fusedsilica to 300 400 400 be mixed (parts by weight) Evaluation Viscosity(Pa · s) 0.35 0.91 0.89 Bending strength 41.2 32.6 33.2 (MPa) Bendingmodulus 7.3 8.3 8.4 (GPa) Linear expansion 17.8 13.5 13.3coefficient(×10⁻⁶/° C.) Water absorption (%) 0.10 0.11 0.10 Dielectric(1 MHz) 2.76 3.02 2.99 constant (100 MHz) 2.77 3.12 3.00 (1 GHz) 2.783.12 3.00 Dielectric (1 MHz) 0.0015 0.0013 0.0012 dissipation (100 MHz)0.0016 0.0015 0.0012 factor (1 GHz) 0.0016 0.0012 0.0015

EXAMPLE 7

A flat plate made of a polymerizable composition and a cured resincomposition was obtained by following the same procedure as that inExample 5 except for using a ruthenium-based metathesis polymerizationcatalyst of Formula (7) as a metathesis polymerization catalyst and 2parts by weight of a polyglycerin polyricinoleate ester (CHIRABAZOLH-818, made by Taiyo Kagaku Co., Ltd.) as a dispersant, and theevaluations similar to Example 1 were carried out. The results ofevaluations were shown in Table 2.

EXAMPLE 8

A flat plate made of a polymerizable composition and a cured resincomposition was obtained by following the same procedure as that inExample 5 except for using a ruthenium-based metathesis polymerizationcatalyst of Formula (8) as a metathesis polymerization catalyst and 2parts by weight of a polyglycerin polyricinoleate ester (CHIRABAZOLH-818, made by Taiyo Kagaku Co., Ltd.) as a dispersant, and theevaluations similar to Example 1 were carried out. The results ofevaluations were shown in Table 2.

COMPARATIVE EXAMPLE 1

A mixture of 80 parts by weight of dicyclopentadiene (made by MaruzenPetrochemical Co., Ltd.) and 20 parts by weight of tricyclopentadiene(made by Maruzen Petrochemical Co., Ltd.) was used as a norbornene-basedmonomer, and a polymerization catalyst solution, which was formed bydissolving 10 parts by weight of a ruthenium-based metathesispolymerization catalyst of Formula (8) in 200 parts by weight of tolueneas a metathesis polymerization catalyst, was added thereto at 25° C. insuch a manner that the rate of the metathesis polymerization catalyst is0.0001 mol % with respect to the norbornene-based monomer, and thismixture was stirred to obtain a polymerizable composition.

The resulting polymerizable composition was poured into a flat platemold and then cured by being heated at 40° C. for 1 hour and 120° C. for1 hour to prepare a flat plate made of a cured resin composition.

With respect to the resulting flat plate made of the polymerizablecomposition and the cured resin composition, the evaluations similar toExample 1 were carried out. The results of evaluations were shown inTable 2.

COMPARATIVE EXAMPLE 2

A substance, which is formed by adding 5 parts by weight of a curingagent (isocyanuric acid adduct 2MA-OK, made by Shikoku Corp.) to 100parts by weight of an epoxy resin (bisphenol A RE-310S, made by NIPPONKAYAKU CO., Ltd.), was poured into a flat plate mold and then cured bybeing heated at 100° C. for 2 hours and 150° C. for 3 hours to prepare aflat plate made of a cured resin composition.

With respect to the flat plate made of the epoxy resin and the curedresin composition, the evaluations similar to Example 1 were carriedout. The results of evaluations were shown in Table 2.

COMPARATIVE EXAMPLE 3

Into 100 parts by weight of an epoxy resin (bisphenol A RE-310S, made byNIPPON KAYAKU CO., Ltd.), 5 parts by weight of a curing agent(isocyanuric acid adduct 2MA-OK, made by Shikoku Corp.) and 2 parts byweight of a titanate-based coupling agent (PLENACT KR46B, made byAjinomoto Fine-Techno Co., Ltd.) as a dispersant were blended and theblended mixture was mixed and stirred. Next, 400 parts by weight offused silica (FB-24, made by DENKI KAGAKU KOGYO KABUSHIKI KAISHA,average particle diameter: 18 μm) was blended under stirring to obtain apolymerizable composition.

The resulting polymerizable composition was poured into a flat platemold and then cured by being heated at 100° C. for 2 hour and 150° C.for 3 hours to prepare a flat plate made of a cured resin composition.

With respect to the resulting flat plate made of the polymerizablecomposition and the cured resin composition, the evaluations similar toExample 1 were carried out. The results of evaluations were shown inTable 2.

COMPARATIVE EXAMPLE 4

A mixture of 80 parts by weight of dicyclopentadiene (made by MaruzenPetrochemical Co., Ltd.) and 20 parts by weight of tricyclopentadiene(made by Maruzen Petrochemical Co., Ltd.) was used as a norbornene-basedmonomer, and into this norbornene-based monomer mixture, 2 parts byweight of a silane coupling agent (SILA-ACE S210, made by CHISSO CORP.)was blended as a dispersant and the blended mixture was mixed andstirred. Next, 300 parts by weight of calcium carbonate having anaverage particle diameter (an average particle diameter refers to adiameter at a cumulative-weight of 50% of a particle size distribution)of 12 μm was blended under stirring. Further, a polymerization catalystsolution, which was formed by dissolving 10 parts by weight of aruthenium-based metathesis polymerization catalyst of Formula (8) in 200parts by weight of toluene as a metathesis polymerization catalyst, wasadded thereto at 25° C. in such a manner that the rate of the metathesispolymerization catalyst is 0.0001 mol % with respect to thenorbornene-based monomer, and this mixture was stirred to obtain apolymerizable composition.

The resulting polymerizable composition was poured into a flat platemold and then cured by being heated at 40° C. for 1 hour and 120° C. for1 hour to prepare a flat plate made of a cured resin composition.

With respect to the resulting flat plate made of the polymerizablecomposition and the cured resin composition, the evaluations similar toExample 1 were carried out. The results of evaluations were shown inTable 2.

COMPARATIVE EXAMPLE 5

A mixture of 80 parts by weight of dicyclopentadiene (made by MaruzenPetrochemical Co., Ltd.) and 20 parts by weight of tricyclopentadiene(made by Maruzen Petrochemical Co., Ltd.) was used as a norbornene-basedmonomer, and into this norbornene-based monomer mixture, 2 parts byweight of a silane coupling agent (SH6040, made by Dow Corning ToraySilicone Co., Ltd.) was blended as a dispersant and the blended mixturewas mixed and stirred. Next, 400 parts by weight of calcium carbonatehaving an average particle diameter (an average particle diameter refersto a diameter at a cumulative-weight of 50% of a particle sizedistribution) of 12 μm was blended under stirring. Further, apolymerization catalyst solution, which was formed by dissolving 10parts by weight of a ruthenium-based metathesis polymerization catalystof Formula (8) in 200 parts by weight of toluene as a metathesispolymerization catalyst, was added thereto at 25° C. in such a mannerthat the rate of the metathesis polymerization catalyst is 0.0001 mol %with respect to the norbornene-based monomer, and this mixture wasstirred to obtain a polymerizable composition.

The resulting polymerizable composition was poured into a flat platemold and then cured by being heated at 40° C. for 1 hour and 120° C. for1 hour to prepare a flat plate made of a cured resin composition.

With respect to the resulting flat plate made of the polymerizablecomposition and the cured resin composition, the evaluations similar toExample 1 were carried out. The results of evaluations were shown inTable 2. TABLE 2 Comparative Comparative Example 7 Example 8 Example 1Example 2 Composition Monomer Dicyclopentadiene/ Dicyclopentadiene/Dicyclopentadiene/ Epoxy tricyclopentadiene tricyclopentadienetricyclopentadiene Catalyst Formula (7) Formula (8) Formula (8) —Dispersant CHIRABAZOL CHIRABAZOL — — H-818 H-818 Fused silica FB-24FB-24 — — Amount of fused 400 400 — — silica to be mixed (parts byweight) Evaluation Viscosity(Pa · s) 0.9 0.95 0.02 0.55 Bending strength33.5 31.2 90.1 129.2 (MPa) Bending modulus 8.3 8.3 2.1 3.1 (GPa) Linearexpansion 13.1 14.0 72.2 68.1 coefficient (×10⁻⁶/° C.) Water absorption0.09 0.11 0.11 1.95 (%) Dielectric (1 MHz) 2.98 2.95 3.12 3.82 constant(100 MHz) 2.95 2.94 3.10 3.87 (1 GHz) 2.91 2.98 3.13 3.78 Dielectric (1MHz) 0.0013 0.0015 0.0012 0.0150 dissipation (100 MHz) 0.0013 0.00160.0012 0.0156 factor (1 GHz) 0.0014 0.0015 0.0017 0.0153 ComparativeComparative Comparative Example 3 Example 4 Example 5 CompositionMonomer Epoxy Dicyclopentadiene/ Dicyclopentadiene/ tricyclopentadienetricyclopentadiene Catalyst — Formula (8) Formula (6) Dispersant PLENACTSILA-ACE S210 SILA-ACE S210 KR46B Fused silica FB-24 — — Amount of fused400 300(calcium 400(calcium silica to be mixed carbonate) carbonate)(parts by weight) Evaluation Viscosity(Pa · s) 35 14 20 Bending strengthUnmeasurable Unmeasurable Unmeasurable (MPa) Bending modulusUnmeasurable Unmeasurable Unmeasurable (GPa) Linear expansionUnmeasurable Unmeasurable Unmeasurable coefficient (×10⁻⁶/° C.) Waterabsorption Unmeasurable Unmeasurable Unmeasurable (%) Dielectric (1 MHz)Unmeasurable Unmeasurable Unmeasurable constant (100 MHz) UnmeasurableUnmeasurable Unmeasurable (1 GHz) Unmeasurable Unmeasurable UnmeasurableDielectric (1 MHz) Unmeasurable Unmeasurable Unmeasurable dissipation(100 MHz) Unmeasurable Unmeasurable Unmeasurable factor (1 GHz)Unmeasurable Unmeasurable Unmeasurable

EXAMPLE 9

A flat plate made of a polymerizable composition and a cured resincomposition was obtained by following the same procedure as that inExample 3 except for blending 700 parts by weight of FB550 (made byDENKI KAGAKU KOGYO KABUSHIKI KAISHA, average particle diameter: 11.2 μm)instead of 300 parts by weight of FB-24 as a fused silica, and theevaluations thereof were carried out. The results of evaluations wereshown in Table 3.

EXAMPLE 10

A flat plate made of a polymerizable composition and a cured resincomposition was obtained by following the same procedure as that inExample 3 except for blending 800 parts by weight of FB550 (made byDENKI KAGAKU KOGYO KABUSHIKI KAISHA, average particle diameter: 11.2 μm)instead of 300 parts by weight of FB-24 as a fused silica, and theevaluations thereof were carried out. The results of evaluations wereshown in Table 3.

EXAMPLE 11

A flat plate made of a polymerizable composition and a cured resincomposition was obtained by following the same procedure as that inExample 3 except for blending 800 parts by weight of FB940 (made byDENKI KAGAKU KOGYO KABUSHIKI KAISHA, average particle diameter: 14.9 μm)instead of 300 parts by weight of FB-24 as a fused silica, and theevaluations thereof were carried out. The results of evaluations wereshown in Table 3.

EXAMPLE 12

A flat plate made of a polymerizable composition and a cured resincomposition was obtained by following the same procedure as that inExample 10 except for using a ruthenium-based metathesis polymerizationcatalyst of Formula (8) as a metathesis polymerization catalyst, and theevaluations thereof were carried out. The results of evaluations wereshown in Table 3.

EXAMPLE 13

A flat plate made of a polymerizable composition and a cured resincomposition was obtained by following the same procedure as that inExample 10 except for using a ruthenium-based metathesis polymerizationcatalyst of Formula (10) as a metathesis polymerization catalyst, andthe evaluations thereof were carried out. The results of evaluationswere shown in Table 3. TABLE 3 Example 9 Example 10 Example 11 Example12 Example 13 Composition Monomer Dicyclopentadiene/ Dicyclopentadiene/Dicyclopentadiene/ Dicyclopentadiene/ Dicyclopentadiene/tricyclopentadiene tricyclopentadiene tricyclopentadienetricyclopentadiene tricyclopentadiene Catalyst Formula (7) Formula (7)Formula (7) Formula (8) Formula (10) Dispersant CHIRABAZOL CHIRABAZOLCHIRABAZOL CHIRABAZOL CHIRABAZOL H-818 H-818 H-818 H-818 H-818 Fusedsilica FB-550 FB-550 FB-940 FB-550 FB-550 Amount of fused silica to 700800 800 800 800 be mixed (parts by weight) Evaluation Viscosity(Pa · s)1.94 3.10 3.20 1.94 1.94 Bending strength 34.2 55.0 24.4 34.0 34.5 (MPa)Bending modulus 14.0 16.6 15.0 14.2 14.3 (GPa) Linear expansion 12.111.4 11.8 10.0 10.1 coefficient(×10⁻⁶/° C.) Water absorption(%) 0.0050.007 0.005 0.005 0.005 Dielectric (1 MHz) 3.15 3.24 3.21 3.22 3.18constant (100 MHz) 3.18 3.26 3.19 3.25 3.18 (1 GHz) 3.19 3.26 3.19 3.223.24 Dielectric (1 MHz) 0.0023 0.0029 0.0028 0.0026 0.0022 dissipation(100 MHz) 0.0021 0.0026 0.0028 0.0023 0.0025 factor (1 GHZ) 0.00250.0028 0.0029 0.0027 0.0026

INDUSTRIAL APPLICABILITY

In accordance with the present invention, it is possible to provide thepolymerizable composition and the cured resin composition, linearexpansion coefficients of which are significantly improved withoutimpairment of the excellent properties such as the heat resistance andthe mechanical strength of norbornene-based resins.

1. (canceled)
 2. A polymerizable composition, which comprises apolymerizable substance containing a norbomene-based monomer or oligomeras a main component, a metathesis polymerization catalyst and silicapowder, the silica powder being contained in an amount of 200 parts byweight or more with respect to 100 parts by weight of the polymerizablesubstance and, further comprises at least one kind selected from thegroup consisting of a glycerin fatty acid ester, a polyglycerinpolyricinoleate ester and a titanate-based coupling agent.
 3. Thepolymerizable composition according to claim 2, wherein the silicapowder is a surface treatment silica surface-treated with a fatty acidor a fatty acid ester.
 4. The polymerizable composition according toclaim 2, wherein the silica powder is contained in an amount of 200 to1,000 parts by weight with respect to 100 parts by weight of thepolymerizable substance.
 5. A cured resin composition, which has acrosslinking structure formed by curing the polymerizable compositionaccording to claim 2, the average linear expansion coefficient at atemperature of 20 to 100° C. being 3×10⁻⁵/° C. or less.
 6. A cured resincomposition, which has a crosslinking structure formed by curing apolymerizable composition comprising a polymerizable substancecontaining a norbomene-based monomer or oligomer as a main component,the average linear expansion coefficient at a temperature of 20 to 100°C. being 3×10⁻⁵/° C. or less, the bending strength measured according toa method specified in JIS K 7055 being 15 GPa or more, and thedielectric constant being 3.5 or less.
 7. The cured resin compositionaccording to claim 6, wherein the water absorption after immersing for24 hours in water of 23° C. is 1% by weight or less.
 8. Thepolymerizable composition according to claim 3, wherein the silicapowder is contained in an amount of 200 to 1,000 parts by weight withrespect to 100 parts by weight of the polymerizable substance.
 9. Acured resin composition, which has a crosslinking structure formed bycuring the polymerizable composition according to claim 4, the averagelinear expansion coefficient at a temperature of 20 to 100° C. being3×10⁻⁵/° C. or less.
 10. A cured resin composition, which has acrosslinking structure formed by curing the polymerizable compositionaccording to claim 4, the average linear expansion coefficient at atemperature of 20 to 100° C. being 3×10⁻⁵/° C. or less.